JPH02217857A - Photosensitive resin composition and photosensitive element - Google Patents

Abstract

PURPOSE:To allow the development by a fire retardant developing soln. and to provide an excellent resolution, heat resistance and surface brightness by incorporating a photopolymerizable unsatd. compd. obtd. by bringing isocyanate ethyl methacrylate into reaction with the secondary hydroxyl group of an unsatd. compd. obtd. by being subjected to a specific addition reaction into the above compsn. CONSTITUTION:This compsn. contains the photopolymerizable unsatd. compd. obtd. by bringing the isocyanate ethyl methacrylate at the isocyanate equiv./hydroxyl group equiv. ratio adjusted in a 0.1 to 1.2 range into reaction with the secondary hydroxyl group of the unsatd. compd. obtd. by the addition reaction of one or 2 kinds of novolak type epoxy resins and unsatd. carboxylic acids at the acid equiv./epoxy equiv. ratio adjusted in a 0.1 to 0.98 range. A compd. having at least one epoxy group, 2- methyl-[4-(methylthio)phenyl]-2-morpholino-1-propane, fine granular packing agent, and a heating hardener are incorporated into this compd. The photosensitive resin compsn. which can be developed by the fire retardant developing soln., and has the excellent resolution, heat resistance, surface brightness, and blanking property with a thick film is obtd. in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a photosensitive resin composition and a photosensitive element for forming a protective film used in printed wiring board production, metal precision processing, and the like.

(Prior Art) Photosensitive resin compositions having excellent properties that can be used as solder masks, resists for chemical plating, and the like have been known in the printed wiring board industry.

The main purpose of a solder mask is to limit the soldering area during soldering, to prevent solder bridging, etc., to prevent corrosion of bare copper conductors, and to maintain electrical insulation between conductors over a long period of time. Is Rukoto.

By the way, solder masks are usually made of epoxy resin,
A mask (printed mask) whose product is a thermosetting resin such as aminoblast resin is used.

However, in recent years, the density of wiring on printed wiring boards has increased, and the requirements for electrical insulation between conductors have also become stricter, and the solder masks used for them are also required to be thick and have excellent dimensional accuracy. Screen printing methods can no longer cope with this problem.

Therefore, the photographic method (forming an image by imagewise exposure followed by development) has been used to create a thick film (usually 25 μm on a conductor is desired) with excellent resolution (dimensional accuracy) and high reliability (heat resistance, stun kneading properties, etc.). ) There is a desire for a photosensitive resin composition that can form a solder mask and that is less likely to cause cracks in a press punching machine.

Conventionally, as a photosensitive resin composition for forming a solder mask,
For example, (1) a photosensitive resin composition containing an acrylic polymer and a photopolymerizable monomer as main components (JP-A-53-56018, JP-A-54-1018, etc.); (2) photoreactivity; A photosensitive resin composition containing an applied epoxy resin and an epoxy resin curing agent as main components (Japanese Patent Application Laid-Open No. 52-37996
No. 1, JP-A-58-62636, JP-A-62-
74920, etc.), (3) Isocyanatoethyl methacrylate-modified photosensitive resin composition (Japanese Unexamined Patent Publication No. 132947/1983), and the like are known.

(Problems to be Solved by the Invention) However, the photosensitive resin composition of (1) above cannot be used for ordinary film-like photosensitive materials for etching and plating (for example, manufactured by DuPont, trade name Riston, manufactured by Hitachi Chemical Co., Ltd.,
The flame retardant 1.
1. Although it can be developed with 1-trichloroethane and can form a high-resolution solder mask, such photosensitive resin compositions use a large amount of acrylic polymer to impart film properties. There is a drawback that the heat resistance of the cured film is not sufficient.

Furthermore, the photosensitive resin compositions described in JP-A-52-37996 and JP-A-58-62636 in (2) above are based on epoxy resins, and the cured film has excellent heat resistance. However, since it is insoluble in flame-retardant organic solvents such as 1,1°1-trichloroethane, it is necessary to use a flammable organic solvent such as cyclohexanone as a developer, which is disadvantageous in terms of safety.

Furthermore, the photosensitive resin composition described in JP-A No. 62-74920 has 1. 1. A flame-retardant developer such as 14-lychloroethane can be used, but it has the disadvantage that it tends to crack during punching.

Furthermore, the photosensitive resin composition of (3) above has a 1°1.1
- It can be developed with a developer such as trichloroethane, has excellent resolution and heat resistance, and when mixed with a talc-based filler as shown in JP-A No. 58-62636, printed wiring boards and cured coatings can be formed. This improves the adhesion to the surface of the film and forms a highly reliable solder mask, but it has the disadvantage that the surface of the film lacks gloss due to damage during development. For this reason, there is a problem that scratches occur due to external factors before being used in final products such as electronic parts, which impairs the commercial value of the solder mask.

In view of the above problems, the present invention has been achieved by: 1. 1. 1-) To form a highly reliable solder mask that can be developed with a flame-retardant developer such as dichloroethane, has a thick film, and has excellent resolution (dimensional accuracy), heat resistance, surface gloss, and punching workability. The purpose of the present invention is to provide a photosensitive resin composition that can be used as a photosensitive resin composition.

(Means for Solving the Problems) The present invention provides (a) one or more novolaks selected from the group consisting of ortho-cresol novolac-type epoxy resins, phenol novolac-type epoxy resins, and halogenated phenol novolak-type epoxy resins; type epoxy resin and unsaturated carboxylic acid at an acid equivalent fl/epoxy equivalent ratio of 0. The isocyanate ethyl methacrylate is reacted with isocyanate ethyl methacrylate to the secondary hydroxyl group of the unsaturated compound obtained by addition reaction in the range of 0.1 to 0.98. 100 parts by weight of the resulting photopolymerizable unsaturated compound, (b) 1 to 50 parts by weight of a compound containing at least one epoxy group, (c) 2-methyl-[4-(methylthio)phenyl]-
A photosensitive resin containing 2-morpholino-1-propane, 2 to 15 parts by weight (d''), ?F111 (10 to 100 parts by weight of a granular filler, and (e) 1 to 15 parts by weight of a heat curing agent). The present invention relates to a composition and a photosensitive element using the same.

The photosensitive resin composition of the present invention has one or more types selected from the group consisting of orthocresol novolac type epoxy resin, phenol novolac type epoxy resin, and halogenated phenol novolac type epoxy resin as essential component (a). A novolac type epoxy resin and an unsaturated carboxylic acid are used at an acid equivalent/epoxy equivalent ratio of 0.
Isocyanate ethyl methacrylate is added to the secondary hydroxyl group of the unsaturated compound obtained by addition reaction in the range of 1 to 0.98 at an isocyanate equivalent/hydroxyl group equivalent ratio of 0.1.
Contains a photopolymerizable unsaturated compound obtained by reaction in the range of 1.2 to 1.2.

The novolak-type epoxy resin used in the present invention is obtained by reacting, for example, orthocresol, phenol, halogenated phenol, etc. with an aldehyde in the presence of an acid catalyst. It is obtained by reacting epichlorohydrin and is commercially available.

Orthocresol novolac type epoxy resins include:
For example, Araldite ECN129 manufactured by Ciba Geigy.
9 (softening point 99°C, epoxy equivalent 230), ECN12
80 (softening point 80℃, epoxy f12:30), E
CN1273 (softening point 73°C, epoxy equivalent 230)
, manufactured by Nippon Kayaku■, EOCN104 (softening point 90~
100℃, epoxy ff1225-245), ECN
123 (softening point 80-90℃, epoxy equivalent j1215
~235), ECN127 fi215~235), EOCNIOI (softening point 65
-69°C, epoxy 11205-225), etc.

As the phenol novolak type epoxy resin, for example, Epikote 154 (epoxy equivalent: 176 to
181), Dow Chemical Co., DEN431 (epoxy equivalent ff1172-179), DEN438 (epoxy equivalent 175-182), Tobu Kasei ■, YDPN-6
38 (epoxy equivalent 170-190), YDPN-60
1 (epoxy equivalent 180-220), YDPN-602
(epoxy equivalent: 180 to 220).

Examples of halogenated phenol novolac type epoxy resins include BREN (epoxy equivalent: 2
70-300. Bromine content 35-37%, softening point 80-
Examples include brominated phenol novolak type epoxy resins such as 90°C).

Further, as the unsaturated carboxylic acid, acrylic acid, methacrylic acid, β-furylacrylic acid, β-styrylacrylic acid, α-cyanocinnamic acid, cinnamic acid, etc. can be used.

In the present invention, when producing the photopolymerizable unsaturated compound (a), the addition reaction between these novolac type epoxy resins and unsaturated carboxylic acids is carried out by a conventional method, as shown in formula (1), acid equivalent/epoxy This is carried out with the equivalent ratio in the range of 0.1 to 0.98.

When the acid equivalent/epoxy equivalent ratio is less than 0.1, the photocured film is likely to swell during development treatment after image exposure. If the acid equivalent/epoxy equivalent ratio exceeds 0.98, adhesiveness, heat resistance, etc. will decrease.

The addition reaction between a novolac type epoxy resin and an unsaturated carboxylic acid is a well-known reaction, and can be easily carried out by appropriately setting the conditions. Dissolve in an inert solvent such as cellosolve acetate or cyclohexanone, and use as a catalyst a tertiary amine such as triethylamine, trilobylamine, diethylcyclohexylamine, or a quaternary ammonium salt such as benzyltrimethylammonium chloride or benzyltriethylammonium chloride. In addition, using hydroquinone, p-methoxyphenol, etc. as a polymerization inhibitor,
An addition reaction can be carried out by stirring and reacting with the above unsaturated carboxylic acid at 70 to 110°C in the above equivalent ratio range, and (a) the unsaturated compound which is the precursor of the photopolymerizable unsaturated compound is Obtainable.

The reaction of isocyanate ethyl methacrylate with the secondary hydroxyl group of the unsaturated compound obtained by addition-reacting the above-mentioned novolac type epoxy resin with an unsaturated carboxylic acid is carried out by a conventional method as shown in formula (2), isocyanate equivalent/hydroxyl group. This is carried out with the equivalent ratio in the range of 0.1 to 1.2.

The isocyanate equivalent/hydroxyl group equivalent ratio is 0. If it is less than 1, ], 1. Development with flame-retardant organic solvents such as 1-trichloroethane becomes difficult, and photocurability also decreases. Isocyanate equivalent/hydroxyl group equivalent ratio is 1,
If it exceeds 2, gelation tends to occur during the reaction, and properties such as heat resistance also deteriorate. After the reaction, it is desirable for safety and to improve storage stability to urethane and deactivate the remaining incyanatoethyl methacrylate using a primary alcohol such as methanol, ethanol, or 2-hydroxyethyl methacrylate.

Isocyanate ethyl methacrylate is a compound represented by, for example, those manufactured by Dow Chemical Company and those manufactured by Showa Ropeia Company are used.

The reaction of isocyanatoethyl methacrylate to hydroxyl groups is a known reaction, and can be easily carried out by appropriately setting the conditions. By adding a urethanization catalyst such as dibutyltin dilaurate or dibutyltin di-2-ethylhexoate to this product (unsaturated compound), and stirring and reacting isocyanate ethyl methacrylate at 50 to 110°C within the above equivalent ratio range. , (a) a photopolymerizable unsaturated compound can be obtained. Under such reaction conditions, side reactions such as the reaction between urethane bonds and epoxy groups and thermal polymerization of unsaturated bonds can be prevented, and as a result, gel-like substances are not formed ((a) A polymerizable unsaturated compound can be obtained.

In the present invention, particularly preferred (a) photopolymerizable unsaturated compound is an orthocresol novolac type epoxy resin/acrylic acid/isocyanatoethyl methacrylate based reaction product (acid equivalent/epoxy equivalent ratio 0.1 to 0.98).
, isocyanate equivalent/hydroxyl group equivalent ratio 0.1 to 1.2) Orthocresol novolac type epoxy resin/methacrylic acid/isocyanate ethyl methacrylate based reactant (
The acid equivalent/epoxy equivalent ratio is 0.1 to 0.98, the isocyanate equivalent/hydroxyl equivalent ratio is 0.1 to 1.2), and the like.

The photosensitive resin composition of the present invention contains a compound having at least one epoxy group as an essential component (b).

As a compound having at least one epoxy group, for example, a compound represented by the following formula (3)...(3) Coat 1010 (Epoxy per ff
0, average molecular ff15500), etc.

Next, the photosensitive resin composition of the present invention has an essential component (c
), 2-methyl-[4-
(Methylthio)phenyl-2-morpholino-1-propane is contained as a photopolymerization initiator.

) The weight average molecular weight of these compounds is 3000 to 100
The range is preferably 00, more preferably 3500 to 60
The range is 00.

Examples of the above-mentioned compounds include, for example, Epicoat 1009 manufactured by Yuka Shell Epoxy (epoxy equivalent: 2400 to 3).
300. average molecule ff13750), shrimp 2-methyl-
[4-(methylthio)phenyl-2-morpholino-
1-Propane is available from Ciba Geigy, for example, by IRGA.
Commercially available as CURE907.

The essential component (c) used in the present invention may be used alone, but may include substituted or unsubstituted polynuclear quinones, such as
Ketoaldonyl compounds such as 2-ethylanthraquinone, 2-1-butylanthraquinone, octamethylanthraquinone, 11,2-benzanthraquinone, 2°3-diphenylanthraquinone, diacetylbenzyl, and benzoin.

α-ketoaldonyl alcohols and ethers such as pyrone, α-hydrocarbon-substituted aromatic acyloins such as α-phenyl-benzoin, α,α-jethoxyacetophenone, benzophenone, 4.4′-bisdialkylamino Aromatic ketones such as benzophenone, 2-methylthioxanthone, 2,4-diethylthioxanthone, 2
- It may be used in combination with one or more thioxanthone sensitizers such as chlorothioxanthone, 2-isopropylthioxanthone, and 2-ethylthioxanthone.

Next, the photosensitive resin composition of the present invention contains a fine particulate filler as an essential component (d).

As the particulate filler, for example, talc, silica, titanium oxide, clay, calcium carbonate, hydrated silicic acid, aluminum hydroxide, alumina, barium sulfate, antimony trioxide, magnesium carbonate, mica powder, aluminum silicate, magnesium silicate, etc. are used. It will be done.

The particle size of the particulate filler is preferably 0.01 to 10 μm, more preferably 0.01 to 1.5 μm, from the viewpoint of preventing deterioration of resolution, adhesion of the cured film, and the like. It is preferable that the particulate filler is uniformly dispersed in the photosensitive resin composition.

In addition, in order to increase the adhesive strength between the filler and the photopolymerizable unsaturated compound, the surface of the filler is treated with a silane coupling agent having functional groups such as hydroxyl groups, amino groups, epoxy groups, and vinyl groups. You can also. Examples of the silane coupling agent include γ-aminopropyltriethoxysilane, β-aminoethyl-γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane. Can be mentioned.

The photosensitive resin composition of the present invention also contains a heating curing agent as an essential component (e).

Examples of heat curing agents include dicyandiamide, boron trifluoride monoethylamine complex, 2-methylimidazole, 2-heptadecyl imidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-
2-phenylimidazole, 1-cyanoethyl-2-methylimidazole trimellitate, 1-cyanoethyl-
2-Undecyl imidazole trimellitate, 2.4-
Diamino-6-[2”-methyl-imidazole-(1)
i -ethyl-1,3,5-)riazine, 2,4-diamino-6-[2=-ethyl-4'methylimidazolyl-
(1)”]-]ethyl-1,35-triazine, 2.4
-di,amino-6-[2-undecyl-imidazolyl-(1)"]-]ethyl-1 3.5-1 riazine and the like.

In the photosensitive resin composition of the present invention, 1 to 51 parts by weight of the compound (b) having at least one epoxy group is added to 100 parts by weight of the photopolymerizable unsaturated compound (a), 2-methyl -[4-(methylthio)phenyl]-2
- Use 2 to 15 parts by weight of morpholino-1-propane (c), 10 to 100 ffiflt parts of particulate filler (d) and 1 to 15 parts of heat curing agent (e) in a two-part seedling enclosure.

In the present invention, if component (b) is less than type 1 seedling, the punching processability will be poor, and if it exceeds 50 parts by weight, it will be difficult to develop. If component (c) is less than 2 parts, the photocurability is poor, and if it exceeds 15 parts, the surface hardens too quickly and the inside becomes difficult to harden.

If component (d) is less than 10 parts by weight, the residual strain during curing shrinkage is large and cracks and peeling are likely to occur, and if it exceeds 100 parts by weight, the particles are likely to be exposed on the surface after development.
Poor water resistance and gloss.

The amount of component (e) is in the range of 1 to 15 parts by weight from the viewpoint of epoxy group reactivity, solvent resistance, and development residue.

Moreover, the photosensitive resin composition of the present invention may contain other photopolymerizable compounds.

Examples of other light-combining compounds include trimethylolpropane triacrylate, pentaerythritol triacrylate, trimethylhexamethylene diisocyanate/2-hydroxyethyl acrylate (1/2 molar ratio) reaction product, isocyanate ethyl methacrylate/water (
2/1 molar ratio) reactants, etc.

Furthermore, photopolymerizable compounds disclosed in JP-A-53-56018 can also be used. However, the inclusion of these other photopolymerizable compounds is necessary for maintaining heat resistance (a)
The amount is preferably 10% by weight or less based on the photopolymerizable unsaturated compound.

Furthermore, the photosensitive resin composition of the present invention may contain other subsidiary components. Secondary components include polymer binders, thermal polymerization inhibitors, dyes, pigments, coating properties improvers, antifoaming agents,
Examples include flame retardants and adhesion improvers.

The photosensitive resin composition of the present invention can be applied directly onto a substrate to be processed and protected by conventional methods such as dip coating, flow coating, and screen printing to easily form a photosensitive layer with a thickness of 10 to 150 μm. Can be done. If necessary, the composition can be dissolved in a solvent for coating.

Examples of the solvent include acetone, methyl ethyl ketone, methyl cellosolve acetate, ethyl cellosolve acetate, cyclohexanone, methyl cellosolve, methylene chloride, 1,1,1-trichloroethane, and mixtures thereof.

In addition, this solution is applied onto a film such as a polyethylene terephthalate film or a polyimide film by a knife coating method or a roll coating method, and the photosensitive element obtained by drying is heated and pressed onto a substrate using a hot roll. A photosensitive layer can also be formed by laminating them. At this time, the substrate is a printed wiring board or the like on which conductor wiring lines are formed.
When the layers have irregularities of 0 μm or more, it is preferable to laminate them under a vacuum of 200 mmHg or less in order to prevent air from being entrained. As a device for this purpose, for example,
A laminating apparatus described in Japanese Patent No. 5-13341 is used. In addition, when using a support film that is opaque to actinic light, it is necessary to peel off the support film at the time of exposure.

Exposure and development of the photosensitive layer thus formed are carried out by conventional methods. In other words, an ultra-high pressure mercury lamp as a light source,
Using a high-pressure mercury lamp or the like, the layer of the photosensitive resin composition is imagewise exposed directly or through a negative mask through a transparent film such as a polyethylene terephthalate film. If a transparent film remains after exposure, it is peeled off and developed.

As a developer, for example, 1. 1. 14 Lichloroethane, alcohol denatured 1. 1. 1-) Lichloroethane, Suririn EX-R (manufactured by Toagosei Kagaku Co., Ltd.), and Eterna IR (manufactured by Asahi Kasei Industries, Ltd.).

The image-like protective film obtained by the above method has properties as a corrosion-resistant film for ordinary etching, plating, etc., but after development, exposure to active light and heat treatment at 80 to 200°C are necessary. By doing this, scratch resistance, adhesion,
It can improve properties such as heat resistance, solvent resistance, and punching workability.
A permanent protective film that satisfies the characteristics of a photosensitive resin composition such as a solder mask can be obtained.

(Example) Next, the present invention will be explained by examples.

Note that in the following, "parts" means "parts by weight J."

Example 1 (a) Synthesis of photopolymerizable unsaturated compound A, orthocresol novolac type epoxy resin, EO
CN-102 (Epoxy F1230) 1095 parts Ethyl cellosolve acetate 800 parts Part B. Lilic acid 69 parts Benzyltrimethylammonium chloride 7 parts p-methoxyphenol 3 parts Ethyl cellosolve acetate 100 parts C, incyanato Ethyl methacrylate 163 parts Dibutyl tin dilaurate 0.5 parts Ethyl cellosolve acetate 100 parts Methanol
The above mixture was added to a 10-part reactor equipped with a thermometer, a stirrer, a condenser tube, and a dropper capable of heating and cooling, and the mixture was heated to 60° C. with stirring to uniformly dissolve the mixture. B was added dropwise thereto over about 1 hour while maintaining the reaction temperature at 60°C. After dropping B, the temperature was raised to 80°C over 2 hours, and stirring was continued at 80°C for about 15 hours until the acid value of the reaction system was brought to 1 or less.

Next, the temperature was lowered to 60°C, and C was uniformly added dropwise over about 3 hours while maintaining the reaction temperature at 60°C. After dropping C, the reaction temperature was gradually raised to 80°C over about 5 hours, and then the temperature was lowered to 60°C, D was added, and stirring was continued for about 1 hour. In this way, orthocresol novolak type epoxy resin with nonvolatile content of 57% by weight/acrylic acid/isocyanatoethyl methacrylate (acid equivalent/epoxy equivalent ratio -
0゜2, isocyanate equivalent fit/hydroxyl group equivalent ratio -1,
1) A solution (1) of a photopolymerizable unsaturated compound was obtained.

(b) Preparation of photosensitive resin composition Solution of photopolymerizable unsaturated compound obtained in (a) (1) 1
75 parts (solid content 100 parts), Ebiko) 1009 (
20 parts (solid content 10 parts) of a solution prepared by dissolving Yuka Shell Epoxy (manufactured by Yuka Shell Epoxy ■) in methyl ethyl ketone to a solid content of 50%, and 2-methyl-[4-(methylthio)phenyl]-2-morpholino- 1-Propane (IRGACURE 907 manufactured by Ciba Geigy) 10 parts, Micro Ace p-4 (Japan Talc ■, ultrafine particle talc, average particle size 1.5 μm) 7 parts, Crystallite 5V (Tatsumori ■, Super 36 parts of fine particle silica (average particle size 5 μm), 0.1 part of phthalocyanine green, 3 parts of 2-methylimidazole, and 0.1 part of Modaburo (manufactured by Mitsubishi Monsando, polymethacrylate leveling agent) were mixed, and mixed with three rolls. A solution of the photosensitive resin composition was prepared by mixing and dispersing.

(c) Formation of a cured film The solution of the photosensitive resin composition obtained in (b) was applied onto a steel-clad laminate (MCL-E-61 manufactured by Hitachi Chemical Co., Ltd.) at room temperature for 20 minutes. Dry for 20 minutes at ℃ to a thickness of 40℃.
A photosensitive layer of μm was formed.

Then, through a negative mask, HMW- manufactured by Oak Seisakusho ■
Exposure was performed using a 201B type exposure machine at 400rr+J/cd. After exposure, the film was heated at 80° C. for 5 minutes, left at room temperature for 30 minutes, and then spray-developed at 20° C. for 60 seconds using Three-One EX-R (manufactured by Toagosei Chemical Co., Ltd.). Then 15
A solder mask with excellent dimensional accuracy corresponding to a negative mask was obtained by heat treatment at 0° C. for 60 minutes.

This solder mask has a glossy surface and excellent punching workability with a shear, and is soldered using rosin-based flux A-226 (manufactured by Tamura Kaken) at 260°C for 10 seconds, and then with Triclean. After cleaning at 25°C for 10 minutes, cracks occurred and the coating peeled off in a thermal shock test of 50 cycles under MIL-8TD-202E107D condition B (-65°C for 30 minutes, room temperature within 5 minutes, 125°C for 30 minutes). was not recognized, indicating that his credibility was very high.

Example 2 (a) Synthesis of photopolymerizable unsaturated compound A, orthocresol novolak type epoxy resin, manufactured by Nippon Kayaku F# Product name EOCN-104 (epoxy resin)
f1230) 920 parts Halogenated phenol novolac type Evokin resin 1 Manufactured by Nippon Kayaku Product name BREN (Epoxy charge 285)
285 parts Methyl cellosolve acetate 600 parts B
Part child. Lyric acid 288 parts Benzyltriethylammonium chloride 7 parts p-methoxyphenol 3 parts Methyl cellosolve acetate 100 parts C, isocyanate Ethyl methacrylate 620 parts Dibutyltin dilaurate 0.5 parts Methyl cellosolve acetate 100 parts, methanol 10 parts Above A- Using D, the other procedures were the same as in Example 1(a), and the nonvolatile content was 54.
Weight% orthocresol novolak type epoxy resin/
Acrylic acid/isocyanate ethyl methacrylate (acid equivalent/epoxy ratio = 0.8, isocyanate n/
Hydroxyl group equivalent ratio -1) Solution of photopolymerizable unsaturated compound (2
) was obtained.

(b) Preparation of photosensitive resin composition The solution of the photopolymerizable unsaturated compound obtained in (a) above (2
) 185 parts (solid content 100 parts), Epicoat 1010
(manufactured by Yuka Shell Epoxy ■) in advance with ethyl cellosolve acetate to a solid content of 50%, 30 parts (solid content 15 parts), 2-methyl-[4-(methylthio)phenyl]-2 -morpholino-1-propane 7
1 part 2-methylthioxanthone, 5 parts Glistalite
Mix and disperse 30 parts of V, 0.02 parts of Victoria Pure Blue, and 2 parts of 2-methylimidazole using three rolls.
A solution of a photosensitive resin composition was prepared.

Hereinafter, in the same manner as in Example 1(c), having surface gloss,
A cured film with excellent heat resistance was obtained due to poor punching workability with a shear.

Example 3 (a) Synthesis of photopolymerizable unsaturated compound A, orthocresol novolak type epoxy resin, YDPN-638 manufactured by Tobu Kasei (epoxy dopant 180)
857 parts ethyl cellosolve acetate 600 parts B, cinnamic acid
176 parts acrylic acid 86
Benzyltrimethylammonium chloride 7 parts p-methoxyphenol 3 parts Ethyl cellosolve acetate 100 parts C, isocyanate Ethyl methacrylate 369 parts Dibutyl tin dilaurate 0.1 part Ethyl cellosolve acetate 100 parts Methanol
Part 1O Using the above A-D, and otherwise in the same manner as in Example 1 (a), orthocresol novolak type epoxy resin/cinnamic acid/acrylic acid/isocyanatoethyl methacrylate (65% by weight nonvolatile content) was prepared.
Acid equivalent/epoxy equivalent ratio = 0.5, Incyanate equivalent f
A solution (3) of a photopolymerizable unsaturated compound (fi/hydroxyl group ratio = 1) was obtained.

(b) Preparation of photosensitive resin composition Solution of photopolymerizable unsaturated compound obtained in (a) (3) 1
54 parts (solid content 100 parts), 10 parts (solid content 5 parts) of a solution in which Epicote 1009 was previously dissolved in acetone so that the solid content was 50 heavy seedlings, Glistalite 2101-
41 (Tatsumori, γ-glycidoxypropyltrimethoxysilane-treated ultrafine silica, average particle size 1 μm) 50 parts, 2-methyl-[4-(methylthio)phenyl]-2-
10 parts of morpholino-1-propane, 1 part of ethyl dimethylamine benzoate, 1 part of phthalocyanine green 0°,
A solution of a photosensitive resin composition was prepared by mixing and dispersing 2 parts of dicyandiamide, 1 part of 2-methylimidazole, and 5 parts of methyl cellosolve using a three-roll roll.

Hereinafter, in the same manner as in Example 1(c), having surface gloss,
A hardened wave pattern with excellent punching workability using a shear and excellent heat resistance was obtained.

Comparative Example 1 The photopolymerizable unsaturated compound solution (1
) 17.5 parts, 10 parts of 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propane, 47 parts of MicroAce p-36 parts of Crystallite 5V,
A cured film obtained in the same manner as in Example 1 (c) was obtained by blending 0.1 part of phthalocyanine green, 3 parts of 2-methylimidazole, and 0.1 part of Modaflow with a three-roll roll. Although it had good gloss and heat resistance, a crack of 3m11 occurred when punched with a shear.

Comparative Example 2 The solution of the photopolymerizable unsaturated compound obtained in Example 1(a) (1
) 175 parts, 50% by weight Epicote 1009 (methyl ethyl ketone solution) 20 parts, benzophenone 10 parts, Micro Ace p-47 parts, Crystallite 5v 36 parts,
0.1 part of phthalocyanine green, 3 parts of 2-methylimidazole, and 0.1 part of Modaflow were mixed and dispersed using three rolls, and a cured film was obtained in the same manner as in Example 1(c). It had good heat resistance, but had no surface gloss.

Comparative Example 3 Solution of the photopolymerizable unsaturated compound obtained in Example 2(a) (2
), 175 parts of 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propane, 1 part of 2-methylthioxanthone, 30 parts of Crystallite 5V, 0.02 part of Victoria Pure Blue, 2 - Mixing and dispersing 2 parts of methylimidazole using three rolls, Example 1
The cured film obtained in the same manner as (c) has surface gloss,
It had excellent heat resistance, but when punched with a shear, 0°2m
A crack of m was generated.

Comparative Example 4 The solution of the photopolymerizable unsaturated compound obtained in Example 3(a) (3
), 50 parts of Crystallite 2101-41, 7 parts of dimethylbenzyl ketal (manufactured by Ciba Geigy, trade name IRGACURE 651), 0.1 part of phthalocyanine green, 2 parts of dianediamide, 2-methylimidazole and methyl cellosolve. A cured film obtained by mixing and dispersing 5 parts with 3 rolls in the same manner as in Example 1(c) had excellent heat resistance, but did not have surface gloss, and had a 0.0. A crack of 6 mm was generated.

(Effects of the Invention) The cured film obtained using the photosensitive resin composition of the present invention has excellent surface gloss, shear punching, heat resistance, and cold shock resistance, so it can be used for etching, plating, etc. It can be used as a permanent protective film for corrosion-resistant films, solder masks, etc.

Moreover, by using the photosensitive resin composition of the present invention, 1. 1. It can be developed with a flame-retardant developer containing 1-trichloroethane as a main component, and it can form a solder mask with excellent resolution, heat resistance, and surface gloss, and it can also form thick-film solder masks etc. using a photographic method. It is also possible.

Furthermore, the film formed using the photosensitive resin composition of the present invention has excellent chemical and physical properties, and is therefore used in interlayer insulation layers of multilayer printed wiring boards, photosensitive adhesives, paints, and plastics. It can also be used for reliefs, printing plate materials, metal precision processing materials, etc.

In addition, this coating is made of tricrene, methyl ethyl ketone,
It has the effect of being sufficiently resistant to organic solvents such as isopropyl alcohol and toluene, and also resistant to acidic or alkaline aqueous solutions.

Claims (1)

[Scope of Claims] 1. (a) One or more novolak-type epoxy resins selected from the group consisting of orthocresol novolac-type epoxy resins, phenol novolac-type epoxy resins, and halogenated phenol novolak-type epoxy resins; Isocyanate ethyl methacrylate is added to the secondary hydroxyl group of an unsaturated compound obtained by addition reaction with a saturated carboxylic acid at an acid equivalent/epoxy equivalent ratio of 0.1 to 0.98. Ga is 0.
(b) Compounds 1 to 5 having at least one epoxy group;
0 parts by weight, (c) 2-methyl-[4-(methylthio)phenyl]-
A photosensitive resin composition comprising: 2-15 parts by weight of 2-morpholino-1-propane; (d) 10-100 parts by weight of a particulate filler; and (e) 1-15 parts by weight of a heat curing agent. 2. A photosensitive element obtained by applying the photosensitive resin composition according to claim 1 onto a film and drying it.